解析 FeIV=HO 物种后续步骤以深入了解铁双氧酶的作用机制。
Insight into the mechanism of an iron dioxygenase by resolution of steps following the FeIV=HO species.
机构信息
Department of Biochemistry and Molecular Biology, Michigan State University, East Lansing, MI 48824, USA.
出版信息
Proc Natl Acad Sci U S A. 2010 Mar 2;107(9):3982-7. doi: 10.1073/pnas.0911565107. Epub 2010 Feb 10.
Abstract
Iron oxygenases generate elusive transient oxygen species to catalyze substrate oxygenation in a wide range of metabolic processes. Here we resolve the reaction sequence and structures of such intermediates for the archetypal non-heme Fe(II) and alpha-ketoglutarate-dependent dioxygenase TauD. Time-resolved Raman spectra of the initial species with (16)O(18)O oxygen unequivocally establish the Fe(IV) horizontal lineO structure. (1)H/(2)H substitution reveals direct interaction between the oxo group and the C1 proton of substrate taurine. Two new transient species were resolved following Fe(IV) horizontal lineO; one is assigned to the nu(FeO) mode of an Fe(III) horizontal line O(H) species, and a second is likely to arise from the vibration of a metal-coordinated oxygenated product, such as Fe(II) horizontal line O horizontal line C(1) or Fe(II) horizontal line OOCR. These results provide direct insight into the mechanism of substrate oxygenation and suggest an alternative to the hydroxyl radical rebinding paradigm.
摘要
铁氧还蛋白生成难以捉摸的瞬态氧物种，以在广泛的代谢过程中催化底物的氧化。在这里，我们解析了典型的非血红素 Fe(II)和α-酮戊二酸依赖性双加氧酶 TauD 中这些中间产物的反应序列和结构。与 (16)O(18)O 氧的初始物种的时间分辨拉曼光谱明确确立了 Fe(IV)水平线 O 结构。(1)H/(2)H 取代揭示了氧基团与底物牛磺酸的 C1 质子之间的直接相互作用。在 Fe(IV)水平线 O 之后解析出两个新的瞬态物种；一个被分配给 Fe(III)水平线 O(H)物种的 nu(FeO)模式，另一个可能源自金属配位的含氧产物的振动，例如 Fe(II)水平线 O 水平线 C(1)或 Fe(II)水平线 OOCR。这些结果提供了对底物氧化机制的直接洞察，并提出了替代羟基自由基再结合范例的可能性。
相似文献
1
Insight into the mechanism of an iron dioxygenase by resolution of steps following the FeIV=HO species.解析 FeIV=HO 物种后续步骤以深入了解铁双氧酶的作用机制。
Proc Natl Acad Sci U S A. 2010 Mar 2;107(9):3982-7. doi: 10.1073/pnas.0911565107. Epub 2010 Feb 10.
2
Steady-state and transient kinetic analyses of taurine/alpha-ketoglutarate dioxygenase: effects of oxygen concentration, alternative sulfonates, and active-site variants on the FeIV-oxo intermediate.牛磺酸/α-酮戊二酸双加氧酶的稳态和瞬态动力学分析：氧浓度、替代磺酸盐和活性位点变体对FeIV-氧中间体的影响。
Biochemistry. 2005 Mar 15;44(10):3845-55. doi: 10.1021/bi048746n.
3
The first direct characterization of a high-valent iron intermediate in the reaction of an alpha-ketoglutarate-dependent dioxygenase: a high-spin FeIV complex in taurine/alpha-ketoglutarate dioxygenase (TauD) from Escherichia coli.α-酮戊二酸依赖性双加氧酶反应中高价铁中间体的首次直接表征：来自大肠杆菌的牛磺酸/α-酮戊二酸双加氧酶（TauD）中的高自旋FeIV复合物。
Biochemistry. 2003 Jun 24;42(24):7497-508. doi: 10.1021/bi030011f.
4
Nuclear Resonance Vibrational Spectroscopic Definition of the Facial Triad Fe═O Intermediate in Taurine Dioxygenase: Evaluation of Structural Contributions to Hydrogen Atom Abstraction.核共振振动光谱学定义牛磺酸双加氧酶中面三角 Fe═O 中间物：对氢原子提取结构贡献的评估。
J Am Chem Soc. 2020 Nov 4;142(44):18886-18896. doi: 10.1021/jacs.0c08903. Epub 2020 Oct 26.
5
O2- and alpha-ketoglutarate-dependent tyrosyl radical formation in TauD, an alpha-keto acid-dependent non-heme iron dioxygenase.在 TauD（一种α-酮酸依赖性非血红素铁双加氧酶）中，氧分子和α-酮戊二酸依赖性酪氨酸自由基的形成。
Biochemistry. 2003 Feb 25;42(7):1854-62. doi: 10.1021/bi026832m.
6
Mechanistic insights on the ortho-hydroxylation of aromatic compounds by non-heme iron complex: a computational case study on the comparative oxidative ability of ferric-hydroperoxo and high-valent Fe(IV)═O and Fe(V)═O intermediates.非血红素铁配合物催化芳香族化合物邻位羟化的机理研究：铁过氧配合物和高价态 Fe(IV)═O 与 Fe(V)═O 中间体相对氧化能力的计算研究案例。
J Am Chem Soc. 2013 Mar 20;135(11):4235-49. doi: 10.1021/ja307077f. Epub 2013 Mar 7.
7
Stopped-flow kinetic analysis of Escherichia coli taurine/alpha-ketoglutarate dioxygenase: interactions with alpha-ketoglutarate, taurine, and oxygen.大肠杆菌牛磺酸/α-酮戊二酸双加氧酶的停流动力学分析：与α-酮戊二酸、牛磺酸和氧气的相互作用
Biochemistry. 1999 Nov 16;38(46):15278-86. doi: 10.1021/bi9912746.
8
Propene activation by the oxo-iron active species of taurine/alpha-ketoglutarate dioxygenase (TauD) enzyme. How does the catalysis compare to heme-enzymes?牛磺酸/α-酮戊二酸双加氧酶（TauD）的氧代铁活性物种对丙烯的活化作用。该催化作用与血红素酶相比如何？
J Am Chem Soc. 2006 Aug 2;128(30):9813-24. doi: 10.1021/ja061581g.
9
Direct detection of oxygen intermediates in the non-heme Fe enzyme taurine/alpha-ketoglutarate dioxygenase.非血红素铁酶牛磺酸/α-酮戊二酸双加氧酶中氧中间体的直接检测
J Am Chem Soc. 2004 Feb 4;126(4):1022-3. doi: 10.1021/ja039113j.
10
Kinetic dissection of the catalytic mechanism of taurine:alpha-ketoglutarate dioxygenase (TauD) from Escherichia coli.大肠杆菌中牛磺酸：α-酮戊二酸双加氧酶（TauD）催化机制的动力学剖析
Biochemistry. 2005 Jun 7;44(22):8138-47. doi: 10.1021/bi050227c.
引用本文的文献
1
Characterization of the Flavin-Dependent Monooxygenase Involved in the Biosynthesis of the Nocardiosis-Associated Polyketide†.参与诺卡氏菌病相关聚酮化合物生物合成的黄素依赖性单加氧酶的特性研究。
Biochemistry. 2024 Nov 5;63(21):2868-2877. doi: 10.1021/acs.biochem.4c00480. Epub 2024 Oct 21.
2
Isonitrile biosynthesis by non-heme iron(II)-dependent oxidases/decarboxylases.非血红素铁(II)依赖的氧化酶/脱羧酶合成异腈。
Methods Enzymol. 2024;704:143-172. doi: 10.1016/bs.mie.2024.06.002. Epub 2024 Jun 29.
3
New Frontiers in Nonheme Enzymatic Oxyferryl Species.非血红素酶氧合铁物种的新前沿。
Chembiochem. 2024 Nov 18;25(22):e202400307. doi: 10.1002/cbic.202400307. Epub 2024 Aug 7.
4
Effects of Clinical Mutations in the Second Coordination Sphere and Remote Regions on the Catalytic Mechanism of Non-Heme Fe(II)/2-Oxoglutarate-Dependent Aspartyl Hydroxylase AspH.第二配位球和远程区域的临床突变对非血红素 Fe(II)/2-氧代戊二酸依赖性天冬氨酸羟化酶 AspH 催化机制的影响。
Chemphyschem. 2024 Sep 16;25(18):e202400303. doi: 10.1002/cphc.202400303. Epub 2024 Jul 30.
5
Unusual catalytic strategy by non-heme Fe(ii)/2-oxoglutarate-dependent aspartyl hydroxylase AspH.非血红素铁（II）/2-氧代戊二酸依赖性天冬氨酸羟化酶AspH的独特催化策略。
Chem Sci. 2024 Feb 5;15(10):3466-3484. doi: 10.1039/d3sc05974j. eCollection 2024 Mar 6.
6
X-ray Spectroscopic Study of the Electronic Structure of a Trigonal High-Spin Fe(IV)═O Complex Modeling Non-Heme Enzyme Intermediates and Their Reactivity.X 射线光谱研究三角高自旋 Fe(IV)═O 配合物模拟非血红素酶中间物及其反应性。
J Am Chem Soc. 2023 Aug 30;145(34):18977-18991. doi: 10.1021/jacs.3c06181. Epub 2023 Aug 17.
7
Correspondence on "Structural Insight into the Catalytic Mechanism of the Endoperoxide Synthase FtmOx1".关于“末端过氧化物合酶 FtmOx1 催化机制的结构见解”的通信。
Angew Chem Int Ed Engl. 2023 Sep 11;62(37):e202218643. doi: 10.1002/anie.202218643. Epub 2023 Aug 4.
8
Catalysis by KDM6 Histone Demethylases - A Synergy between the Non-Heme Iron(II) Center, Second Coordination Sphere, and Long-Range Interactions.KDM6 组蛋白去甲基酶的催化作用 - 非血红素铁(II)中心、第二配位球和远程相互作用之间的协同作用。
Chemistry. 2023 Sep 12;29(51):e202301305. doi: 10.1002/chem.202301305. Epub 2023 Jul 26.
9
A human protein hydroxylase that accepts D-residues.一种可接受D-残基的人源蛋白质羟化酶。
Commun Chem. 2020 May 1;3(1):52. doi: 10.1038/s42004-020-0290-5.
10
Dissecting the Mechanism of the Nonheme Iron Endoperoxidase FtmOx1 Using Substrate Analogues.利用底物类似物剖析非血红素铁内过氧化物酶FtmOx1的作用机制。
JACS Au. 2022 Jun 10;2(7):1686-1698. doi: 10.1021/jacsau.2c00248. eCollection 2022 Jul 25.
本文引用的文献
1
Resonance Raman study of oxyhemerythrin and hydroxomethemerythrin. Evidence for hydrogen bonding of ligands to the iron-oxygen-iron center.氧合蚯蚓血红蛋白和羟基高铁蚯蚓血红蛋白的共振拉曼研究。配体与铁-氧-铁中心氢键作用的证据。
J Am Chem Soc. 1986 Apr 1;108(9):2437-43. doi: 10.1021/ja00269a050.
2
Substrate-triggered formation and remarkable stability of the C-H bond-cleaving chloroferryl intermediate in the aliphatic halogenase, SyrB2.脂肪族卤化酶SyrB2中碳氢键裂解氯高铁中间体的底物触发形成及显著稳定性
Biochemistry. 2009 May 26;48(20):4331-43. doi: 10.1021/bi900109z.
3
C-H bond cleavage with reductants: re-investigating the reactivity of monomeric Mn(III/IV)-oxo complexes and the role of oxo ligand basicity.C-H 键与还原剂的断裂：重新研究单核 Mn(III/IV)-氧配合物的反应性和氧配体碱性的作用。
J Am Chem Soc. 2009 Mar 4;131(8):2762-3. doi: 10.1021/ja8100825.
4
EPR and ENDOR studies of cryoreduced compounds II of peroxidases and myoglobin. Proton-coupled electron transfer and protonation status of ferryl hemes.过氧化物酶和肌红蛋白的低温还原化合物II的电子顺磁共振（EPR）和电子核双共振（ENDOR）研究。高铁血红素的质子耦合电子转移和质子化状态。
Biochemistry. 2008 May 6;47(18):5147-55. doi: 10.1021/bi702514d. Epub 2008 Apr 12.
5
Versatility of biological non-heme Fe(II) centers in oxygen activation reactions.生物非血红素铁（II）中心在氧活化反应中的多功能性。
Nat Chem Biol. 2008 Mar;4(3):186-93. doi: 10.1038/nchembio.71.
6
Non-heme Fe(IV)-oxo intermediates.非血红素铁（IV）-氧中间体
Acc Chem Res. 2007 Jul;40(7):484-92. doi: 10.1021/ar700066p. Epub 2007 Jun 2.
7
Probing the iron-substrate orientation for taurine/alpha-ketoglutarate dioxygenase using deuterium electron spin echo envelope modulation spectroscopy.利用氘电子自旋回波包络调制光谱法探究牛磺酸/α-酮戊二酸双加氧酶的铁-底物取向
Biochemistry. 2007 May 22;46(20):5951-9. doi: 10.1021/bi700562t. Epub 2007 May 1.
8
The diverse and pervasive chemistries of the alpha-keto acid dependent enzymes.α-酮酸依赖性酶的多样且普遍存在的化学性质。
J Biol Inorg Chem. 2007 Jun;12(5):587-601. doi: 10.1007/s00775-007-0231-0. Epub 2007 Apr 13.
9
Two interconverting Fe(IV) intermediates in aliphatic chlorination by the halogenase CytC3.卤化酶CytC3催化脂肪族氯化反应中的两种相互转化的Fe(IV)中间体。
Nat Chem Biol. 2007 Feb;3(2):113-6. doi: 10.1038/nchembio856. Epub 2007 Jan 14.
10
Direct spectroscopic detection of a C-H-cleaving high-spin Fe(IV) complex in a prolyl-4-hydroxylase.脯氨酰-4-羟化酶中碳氢键裂解高自旋铁（IV）配合物的直接光谱检测
Proc Natl Acad Sci U S A. 2006 Oct 3;103(40):14738-43. doi: 10.1073/pnas.0604005103. Epub 2006 Sep 26.
Zotero 插件